Bitumen-treating agent



Patented May 23, 1950 UNITED STATES PATENT OFFICE BITUMEN-TREATIN G AGENT tion of Delaware No Drawing. Application September .6, 1949, Serial No. 114,285

(01. 1os 27a) 16 Claims. 1

This invention relates to the preparation of compositions useful in the art of road-making, and is concerned more particularly with improving the bond between aggregate and bituminous materials. More specifically, the invention pertains to the preparation of bituminous compositions containing a polyamine salt-of an organoe substituted acid of phosphorus, whereby the bond between a bituminous material and wet or dry aggregate may be made stronger, firmer, and more resistant to conditions tending to destroy said bond.

When employing a bituminous substance as a protective or binding material, a constant object sought in the art is the improvement of the adhesive bond between the bitumen and the material, such as aggregate, to be protected therewith or bound thereto. It is desirable to accomplish this object regardless of the type or nature of the material employed or the conditions to which the treated material may be subjected.

Polyamine salts of organoesubstituted inorganic acids broadly are covered in our copending application Serial No. 77,061, filed February 17, 1949, which in turn is .a continuation in part of our abandoned application Serial No. 708,181, filed November 6, .1946.

For example, in the construction of roadways, it is customary to apply bituminous paving materials to .a suitable aggregate, reasonably available near the site of construction. Portions or allot this aggregate may .be of a hydrophilic nature; that is, it is wetted by water in preference to oil. Before the ordinary bituminous paving material is applied to this type of aggregate, itiscustomary to dispel all of the moisture from the aggregate, otherwise a less satisfactory mix is obtained. However, even when the aggregate is dried and a good initial bond is obtained, the unavoidable contact of th bituminouseaggregate composition with normal surface water, rain water, ,and moisture present in the subgrade gradually bring abouta breakdown of the aggregateebituminous material bond. The aggregate is gradually wetted by the water, and the bituminous substance no longer holds the aggregate together, as a result of which a-breakdown of the roadway occurs.

A mb r o s bstances. known as anti-stripping agents, have been propose 11 1 the pu p of strengthening the bond between hydrophilic aggregate and bituminous substances. These substances are incorporated into the bituminous materials and/or the aggregate. However, many of these substances which are of considerable effect for this purpose are relatively expensive'ior use in the large quantities required in new roadway construction or in roadway repair work. Other substances which are more readily available for this purpose and are relatively inexpensive all of the aggregate and thebitumen. Moreover,

it is desirable that the anti-stripping agent be inexpensive, and that it may be used with different types of aggregate of widely varying chemical and physical properties.

Another important property sought in anantistripping agent is stability under adverse conditions of use. For example, it is common practice to maintain. certainliquid asphalts (road oils) and asphaltic cements at temperatures which may range from about200 F. to as highas 56.0 F. or higher to facilitate shipment and use thereof. It is therefore important that the anti-stripping agent be capable of withstanding the h gh temperatures of these materials when incorporated therein.

It is an object of this invention to provide ,a

means of forming .a lasting bond between bituminous subs an es a d m neral ag re ate.

It is a further object of this invention to provide bituminous compositions capable of adherlng firmlyto moist mineralaggregate.

'It isstill a further object of this invention to provide bituminous compositions which will .continue to adhere firmly tomi-neral aggregate.

It is another object of this invention to provide a means of treating mineral aggregate so that a lasting bond may be obtainedbetween bituminous substances and the treated mineral aggregate.

It is also an Object of this invention to provide a relatively inexpensive means for providinga 3 lasting bond between bituminous substances and mineral aggregate.

Still another object of the invention is to provide an anti-stripping agent effective, in small concentrations, to prevent stripping of bituminous substance from aggregate.

Yet another object of the invention is to provide an anti-stripping agent for use in paving mixtures, having superior properties of stability.

Other objects and advantages of the invention will be apparent from the ensuing description'of the invention.

The present invention is based on the discovery that a polyamine salt of organo-substituted acids of phosphorus in combination with a mineral aggregate and a bituminous substance is capable of producing a highly effective bondbetween the aggregate and the bituminous substance.

. 4 solutions or mere stable dispersions of the salt in the bituminous material.

The organo-substituted acids of phosphorus contemplated by the invention are acid-reacting materials capable of forming a salt with the polyamines and include acids of trivalent and pentavalent phosphorus. In addition, the organo-substituted acids of phosphorus are such as contain at least two carbon atoms, and at least one ioniz-- able hydrogen capable of reacting with the polyamines to fcrmthe salt. 'In'genera1,;these materials include compounds characterized by direct carbon-to-acid-forming element bonds, for example, a phosphonate or phosphinate; and compounds having the carbon and acid-forming element linked to an intermediate atom such as oxygen or sulfur, for example, a phosphate or thio- -phosphate.

In our copending application hereinabove referred to, we have disclosed polyamine salts of organo-substituted inorganic acids broadly as I We have now effective anti-stripping agents. found that among the polyamine salts of organo substituted inorganic acids, the polyamine salts of organo-substituted acids of phosphorus are outstanding. These salts, it has been found, may be used in lower concentrations with superior results, as a consequence of which they are considerably less expensive to use in paving mixtures. Moreover, we have found th aforesaid salts to be more effective with a wide variety of aggregate. Also, the polyamine salts of substituted acids of phosphorus have been found to retain their eifectiveness when subjected to most severe conditions of use, and are particularly stable to the high temperatures often encountered in asphaltic mixtures. I

The polyamine salts contemplated by the pli sent invention are such as are formed by the re- .action of an organo-substituted acid of phosphorus, hereinafter to be more fully described, and any organic compound containing at least two amino groups (-NHz) two imino groups (=NI-I) .or an amino and imino group, at least one of which groups is capable of forming salts with acidic substances. Polyamines comprehended by the invention include polyamines referred to in the art as cationic surface active materials, as Well as those polyamines considered to be surface inactive materials. Of these latter materials may be mentioned polyamines having at least two. terminal amino groups, which because of the terminal groups are essentially hydrophllic and are ordinarily considered to be relatively cation surface inactive materials, for example, ethylene diamine; polyamines which, regardless of the position of the amino groups, have terminal carbon chains with fewer than 12 carbon atoms contained therein, that is, terminal chains having a carbon content below the minimum considered to be necessary in such chains in order to impart surface activity to the mo1ecu1e,'f0r example, 2,5-

diamino dodecane; and substantially cation sur-..

face inactive polyalkylene polyamines, such as pentamethylene diamine. In general, polyamines included within the scope of the invention may vary from polyamines containing two or more carbon atoms to polyalkylene polyamines containing 60 or more carbon atoms. In carrying out the invention, any polyamine is suitable which when formed into a salt with the substituted acids of phosphorus, the salt may-be dispersed in the bituminous material to formtrue More specific types of organo-substituted acids of phosphorus or phosphonous, phosphinous, and phosphonic and phosphinic acids; the monoand di-esters of phosphoric acid; the mono-esters of phosphonous and phosphonic acids; various sulphur derivatives of the acids of phosphorus, such as mono-thiophosphonous acid, mono-thioester of phosphonous'and phosphonic acids, etc.

The organic substituent of the inorganic acid may be alkyl groups, saturated, unsaturated, or substituted; alkaryl, aryl, 'aryl alkyl, heteroc-yclic, cyclic non-benzencid radicals; andoxygen-containing radicals such as those in'which the hydrogen of a hydroxyl group has been replaced by esterification, etherification, etc. The nature of these organic radicals is such that the salt of the polyamine and organo-substituted acids of phosphorus is soluble in the bituminous substance or, in the absence of the formation of a true solution, may be stably dispersed in the bituminous material. I

Specific examples of the organo-substituted acids of phosphorus which may be employed in accordance with the invention are: ethyl, propyl,

'butyl, amyl, hexyl, and cetyl phosphonous and phorous acid; diethyl, dipropyl, dibutyl, dihexyl,

didodecyl, ditetradecyL-dicetyl, dioctadecyl, and di-(cetylphenyl) esters of phosphorous acid; partially esterified phosphonous acids, such as ethyl,

propyl, butyl, amyl, hexyl, dodecyl, cetyl, and

"octadecylester's of ethyl phosphonous and phenylphosphonous acids; partially esterified acids of 'pentavalent phosphorussu-ch as ethyl, propyl,

butyl, amyl, hexyl, mono-(hexylphenyl), monod0decyl, 'monocetyl, and mono-octadecyl esters of phosphoric acid; and diethyl, dipropyl, dibutyl, dihexyl, didodecyl, ditetradecyl, dicetyl, dioctadecyl esters of 'phosphoricacids; partially esterified phosphonic acids, such" as hexyl, octyl, decyl, dodecyl, tetradecyl, cetyl, and octadecyl esters of ethyl phosphonic acid, etc.

Particularly useful organo-substituted acids of phosphorus which may be employed as saltforming elements in accordance with the invention are the organo-phosphorus compounds having a direct carbon-to-phosphorus linkage obtained in accordance withthe process described in the copending Jensen and Clayton applicat1on, filed Decemberil3, 1946, Serial No. 716,182. According to the aforesaid process, valuable :organoephosphorus compounds may be obtained .by bubbling oxygen through a mixture of phosphorus trichloride .and any of a large class .of hydrocarbons, whereby a reaction mixture containing a .phosphonyl chloride and phosphorus .oxychloride .is obtained. The phosphonyl chloride maybe separated from the phosphorus oxychloride by distillation of the phosphorus oxy- .chloride, whereupon thephosphonm chloride may be converted to a phosphonate by hydrolysis. Among the hydrocarbons that may be used in the preparationof the .phosphonate may be mentioned cycloaliphatic hydrocarbons, such as cy- .clohexane; aliphatic hydrocarbons, such as propane, butane, hexane, octane, .dodecane, and cotadecane; aromatic hydrocarbons substituted b aliphatic or .cycloaliphatic radicals, such as toluene, and cyclohexyl-benzene; mixtures of hydrocarbons, such as gasoline, kerosene, mineral lubricating oil fractions, and paraflin wax, etc.

The method of incorporation of the polyamine salt contemplated by the invention in mixtures of aggregate and bituminous substance is not critical. Thus, a pre-formed salt of a polyamine and an organo-substituted acid of phosphorus may be added to the bituminous substance and/or to the aggregate prior to admixture of the two; or the salt may be formed in situ in either the aggregate or the bituminous substance or both; or the salt-forming elements of polyamine and acid may be added separately or combined in physical mixtures to either or both bituminous substance and aggregate, in which event it is believed that the salt product is formed upon the migration of the salt-forming elements to the interface of aggregate and bituminous substance. By polyamine salt, therefore, it is intended to include the reaction product of the polyamine and organo-substituted acids of phosphorus, as well as mere physical mixtures of the two salt-forming elements.

According to a preferred embodiment of the invention, the salt is prepared prior to the incorporation thereof in the bituminous substance. The salt may be obtained by mixing the polyamine and acid, preferably in the presence of a diluent or solvent, at room temperature or at elevated temperatures to expedite admixture and reaction, but below decomposition temperatures of the reactants and of the final salt product. Upon completion of the reaction, the resulting product may be added as such or after removal of part or all of the diluent or solvent or in otherwise purified form, for example, the salt obtained after subjection of the reaction products to purification methods well known in the art, such as distillation or solvent extraction, etc.

In the preparation of the salt, the polyamine and the acidic substance need not be present in stoichicmetric proportions, an excess of one or the other being permissible. In general, satisfactory materials have been prepared by employing a mol ratio of polyamine to organo-substituted acids of phosphorus varying from about 1:5 to about 5:1.

In practicing this invention, the po1yamine salt of organo-substituted acids of phosphorus may be added to the bituminous substance before the latter is mixed with the aggregate or the aggregate may be separately treated with the polyamine salt. In the event the polyamine salt is mixed first with the bituminous substance, it is sufficient merely to mix the two together with such heating and agitation as may be necessary toproduce a homogeneous blend. When the ag- .gregate is separately treated with the polyaminle salt, the latter may be mixed with the aggregate as such, or the polyamine salt may be dissolved in a solvent, for example, kerosene, before bein mixed with the aggregate, It is also possible to mix the aggregate, :the po1yamine salt and the bituminous substance simultaneously.

In any case, the polyamine salt need be used in only small amounts. Amounts ranging from about 0.05 to about 10 per cent by weight, preferably 0.1 to 2 per cent, of the bituminous substance when the po1yamine salt is added to the bituminous substance; or about 0.001 per cent to about 1 per cent, preferably 0.01 to about 0.5 per cent, of the aggregate, when the ag regate is treated separately with the polyamine salt.

The bituminous materials that may be employed inaccordance with the invention are those employed in the construction and repair of roads. and are normally solid, semi-solid, or viscous liquids at ordinary atmospheric temperatures.

Examples of suitable bituminous substances or bitumens are petroleum or native asphalt; pye us d llates. such as oil-gas. tar. coal tar; pyrogenous residues, such as blown asphalts, sludge asphalts, pressure tars, tar pitch; pyrobitumens, etc. In addition, mixtures of the foregoing materials, aS well as mixtures :or solutions of the aforesaid materials with solvents, such as naphtha, kerosene and stove oils, to give so-called liquid asphalts are also contemplated by the invention.

Of the foregoing materials, petroleum asphalt Produced by steam-r finin y a -mowin y solvent xt acti n met ods. or b a combination of such methods. and having p tration values of about30 to about according to A. s. T. M.

.D5-25 method, is most advantageously us d- Also, but less desirably, oil-in-wat r type emulsions of these and other bituminous materials maybe used. Such-emulsions can beprepared by methods well known in the art and the emulsions may be of the quick-breaking or penetration type or more stable type emulsions, such as slowbreaking or a mixing-type emulsion.

When the bituminous substance is present in the continuous phase, asin unemulsifled asphalts, cut-backs and road oils, it is preferred to add the polyamine salt to the bituminous substance. When the bituminous substance is emulsified in water, the polyamine salt is preferably added to the aggregate.

The following examples illustrate the practice of the invention, but are not to be construed as limiting the invention thereto. In the examples, the parts are by weight, and film retention was determined according to a film-stripping test which was a modification of the standard Nicholson film-stripping test described in the Proceedings of Asphalt Paving Technologist, January 1932, page 43. According to the test used, test samples of approximately 10.0 g. of the mixture of aggregate (limestone, silica, and rhyolite in the examples), bituminous, substance and anti-stripping agent were allowed to cure in an oven at F. for 24 hours. Following the curing period, about 50 g. of the cured mixture was placed in a flask partially filled with distilled water at 140 F. The flask was stoppered and placed in a frame which was rotated in a water bath at 140 F. After 15 minutes of rotation, the appearance of the mixture was reported in terms of estimated area that remained coated at the conclusion of the test. Conven- ;tionally, any aggregate retaining less'than 70 per cent of film is considered to have failed.

Example 1.--The diethylene triamine salt of laurylephosphoric acid was prepared by dissolving parts of lauryl phosphoric acid in 6 parts of kerosene. To this mixture there was then added with stirring 1 part of diethylene triamine.

Film retention results employing an MC-2 liquid asphalt containing the salt'in an amount of l per cent were as follows:

Limestone V Silica V Rhyolite Percent Percent Percent I 100 "90" 90" Example 2.--About 5 parts of hexadecyl phosphonicacid was dispersed in parts of RC-3 asphalt, after which there was added 5 parts of ethylene diamine with stirring until complete dispersion was achieved. An RC-3 liquid asphalt containing 2 per cent of the final mixture gave the following film retention results:

Limestone Silica Rhyolite I Percent Percent Percent Example 3.A polyamine salt of a phosphinic acid was prepared by adding 4 parts of dodecyl phosphinic acid to 2 parts of propylene diamine. Stirring and heatingwere continued until a uniform mixture was obtained. The product so obtained was added in an amount of 1% to 80-3 liquid asphalt heated to about 275 F. to prevent solidification of the additive. Stirring was continued until a uniform dispersion of the additive was eifectedr Film retention results were as fol- IOWS:

Limestone :Silica Rhyolite Percent Percent Percent the two materialswas continued until complete homogeneity was obtained. Film retention results obtained were:

Limestone Silica Rhyolite Percent Percent Percent 100 100' 100 Example 5.(a) A petroleum base oil used for the manufacture of hydraulic fluid (Specification -AN-0-366) was treated'with phosphorus 'tri- 'light creamy textured paste.

chloride and oxygen in the manner outlined in the Jensen and Clayton application hereinabove referred to. A crude hydraulic fluid phosphonic acid of approximately 20 per cent active acid content was obtained. Without separation from the unreacted base oil, the crude phosphonic acid was used as the acid ingredients in the preparation of the anti-stripping compound.

(b) About 33 g. of the crude phosphonic acid from (a) was mixed with 100 g. of kerosene cutter stock and 67 g. of ethylene diamine to form a heavily viscous to gel-like structure.

(0) About 2 g. of the hydraulic oil phosphonic acid-polyamine salt was added to 98 g. of MC-2 liquid asphalt with continued stirring, the product allowed to stand for 24 hours at 140 F., and

then tested for film-stripping properties with the following results:

Limestone Silica Rhyolite Percent Percent Percent Example 6.-Four grams of decamethylene diamine was combined with 96 g. of the hydraulic oil phosphonic acid obtained under (a) of Example 5, The resultant tarry fluid was mixed with MC2 liquid asphalt at 250 F. in the proportion of 1 g. of the tarry fluid to 99 g. of the asphalt. Film-tripping results were as follows:

Limestone Silica Rhyolite Percent Percent Percent Example 7.-About 17 g. of hexaethylene heptamine was added to 2900 g. of kerosene cutter stock. To this mixture there was added with vigforous stirring 83 g. of the hydraulic oil phos- Six-gram portions of this kerosene solution were phonic acid obtained under (a) of Example 5.

added to 100-gram samples of limestone, silica and rhyolite while stirring vigorously in each case. The samples were allowed to stand until drainage was substantially complete. The treated aggregate was then coated with an MC-Z liquid asphalt and tested for film-stripping properties according to the modified Nicholson test hereinabove described. The following results were obr tained:

Limestone Silica Rhyolite Percent Percent Percent 100 90 90 Example 8.About 33 g. of propylene diamine was added to 67 g. of cetyl phosphoric acid which had been heated until about one-half was completely fluid and the remaining portion, soft. At

this point, heating was stopped and the propylene diamine was added with vigorous stirring. When the reaction mixture had started to drop in temperature, but prior to solidification, 200 7g. of

kerosene cutter stock was added slowly to form a V This paste was added with stirring to MCI-2 liquid asphalt in an Film-stripping results The salts herein contemplated need not be added to thebitumen and/or to the aggregate in pure form. For example, in the event a diluent,

Limestone qmca Rh em for example, kerosene, for any or both of the y salt-forming reactants is employed, upon forma- Percent Percent Percent tion of the salt the diluent need not be removed 90 1 100 from the reaction product prior to its use with the bitumen, suiiicient amount of the diluted salt b in us t i l i Efxample 9 .'The saltof the surface active polyi i g ff sa l: in tlfe i inls ed i r o di lgif desired a Octadecan? m? cetyl phos' Conversely, it is often advantageous to prephomc acld w prepared by d'lssolvtng P l Y pare the salts in concentrate form, and in this parts by Welght 9 cetyl l i m 51x form incorporated into either bitumen or aggre- Eg g fg i g tilere 3 gate or both. in the. desired amounts. Such a W1 f g a W par 5 i procedure has the advantage of providing for i g zg ig s g i' f more intimate admixture of the salt and the mare en i resul W an quld asp terial to be treated. Concentrates of hydrocarcontaining. the resultantsalt in an amount of one mm on Such k .as erosene 0r. naphtha, containing per cent wereasfollows. Limestone, 95%, silica, f t 15 t t 0 90% rhy01ite85% -rom abou per cen o as much as 5 per cent, Example 1v0 Ab0ut five parts of hexadecyl by weight, of the salt are quite satisfactory. In phosphonic acid was dispersed in ten parts of additlon tokerosene, other hydrocarbon diluents RC-3=asphalt, after which there was added about or solvents may be employed 1n the prepamt1 n four parts; of, surface active Lmdiamino hexa of theconcentrate. Such materials-includemindecane with stirring until complete dispersion era/1 011s lllbrlcatlng i s and the hire. Examples was achieved An containing two of other diluents are bituminous substances, such percent of thevfinal; mixture gave the following as the so-called. liquid asphaltshereinabove menfilm retention: Results limestone, 90%; silica, f 90%; rhyolite, 80%, This appl cation s a continuation m-part of The following table illustrates the superiority our copendmg apphcafdon' $91191 i in effectiveness of the polyamine salts of organo- February 1949, Whlch turn 18 a 0011151111194- substituted acids of phosphorus as compared with Hon-impart of our copendme application Serial salts of other acids. In all cases, 1 part by weight 703,131, d November 1946, oth ow of diethylene triamine (D. T.) was mixed with 2 abandonedparts of the indicated acid. The resulting mix- Obviously, many d ficatiO S a d Variations ture was then adde t MIC-2 r ad n in a o of the invention as hereinbefore set forth may be centration of 0.25 per cent, and the anti-stripmade without departing from the spirit and scope ping qualities of each salt determined according thereof, and therefore only such limitations to the modified Nicholson test hereinabove deshould be imposed as are indicated in the apscribed. pended claims.

TABLE I Polyamines (diethylene triamine) Film Retention, percent Acid liofifii f'r 5221 3 Lime stone Silica Rhyolite Average 32 11 1-??? ff- 2/1 0. 25 90 9o 90 90 Do 2 1 0. 2a 90 90 so 90- Stearic Acid--- 2/1 0. 25 90 6 60+ Cetyl phenol 2 1 0. 25 so 30 1o 40 Cresylic acids 2/1 0. 25 100 80 30 70 Asphalt sulfonic acids 2 1 0. 25 90 9o 10 60+ Sulfate wood turpentine 2/1 0. 25 so so 30 60+ From the foregoing table, it can be seen that We claim: of all the diethylene triamine salts employed, the 1. A bituminous composition having superior diethylene triamine salts of cetyl phosphonic acid anti-stripping properties consisting essentially and of cetyl phosphoric acid give an average in of a bitumen normally possessing stripping tendfilm retention of about 90 per cent. While the encies and an amount sufficient substantially to diethylene triamine salt of cresylic acids gives lessen stripping of said bitumen of the salt of a an average of per cent, yet its effectiveness polyamine and an organo-substituted acid of is not as general as that of the salts of the orphosphorus having at least two carbon atoms, gano-substituted acids of phosphorus. Similarly, said carbon atoms being linked to said phosphosome of the other salts are shown as being quite rus through an intermediate atom. efiective with some aggregates but very poor with 70 2. A bituminous composition substantially as others. The table thus illustrates the superior described in claim 1, wherein the phosphorus is effectiveness of the salts of the substituted acids pentavalent phosphorus. of phosphorus in that small concentrations of 3. A bituminous composition substantially as such salts may be used with good results over described in claim 1, wherein the intermediate a wide variety of aggregates. atom i oxygen.

r 4. A bituminous composition substantially'as described in claim 3, wherein the phosphorus is pentavalent phosphorus.

p 5. A bituminous composition having superior anti-stripping properties consisting essentially of a bitumen normally possessing stripping tendencies and, intimately dispersible therein, an amount sufficient substantially to lessen stripping of said bitumen of the salt of a polyamine and an organo-substituted acid of phosphorus having at least two carbon atoms. 7

i 6. A bituminous composition substantially as described-in claim 5, wherein the polyamine is a -polyalky1ene polyamine.

7. A-bituminous composition substantially as described in claim 5, wherein the bitumen i asphalt. V v i 8. A bituminous composition substantially as described in claim 5, wherein the salt is present in an amount of about 0.05 to about by weight of the bitumen. V V 9. A bituminous composition substantially as described in claim 5, wherein the salt is present in an amount of about 0.1 to about 2% byweight of the bitumen. p

10. A bituminous composition substantially as described in claim 5, wherein the phosphorus is pentavalent phosphorus.

V '11. A bituminous composition substantially as described in claim 5, wherein the organo-substi- 12 tuted acid of phosphorus is characterized by a direct carbon-to-phosphorus bond.

12. A bituminous composition substantially as described in claim 11, wherein the phosphorus is pentavalent phosphorus, the bitumen is asphalt and the salt is present in an amount of about 0.05 to 10% by weight of the bitumen.

13. A bituminous road construction composition consisting essentially of, in intimate combination, a mineral aggregate, and a bituminous substance, said bituminous substance containing about 0.05 to 10%, by'weight of the bituminous substanca'of the salt of a polyamine and an organo-substitutedacid of phosphorus. V 14. A bituminous road construction composition substantially as described in claim 13, wherein the polyamine is a polyalkylene polyamine.

15. A bituminous road construction composie tion substantially as described in claim 13, wherein the bituminous substance is asphalt.

"16. A bituminous road construction composition substantially as described in claim 13, wherein the'organo-substituted acid of phosphorus is characterized by a direct carbon-to-phosphorus bond, the phosphorus is pentavalent and the bituminous substance is asphalt.

VAUGHN R. SMITH. DON E. STEVENS.

No references cited. 

1. A BITUMINOUS COMPOSITION HAVING SUPERIOR ANTI-STRIPPING PROPERTIES CONSISTING ESSENTIALLY OF A BITUMEN NORMALLY POSSESSING STRIPPING TENDENCIES AND AN AMOUNT SUFFICIENT SUBSTANTIALLY TO LESSEN STRIPPING OF SAID BITUMEN OF THE SALT OF A POLYAMINE AND AN ORGANO-SUBSTITUTED ACID OF PHOSPHORUS HAVING AT LEAST TWO CARBON ATOMS, SAID CARBON ATOMS BEING LINKED TO SAID PHOSPHORUS THROUGH AN INTERMEDIATE ATOM. 